Charge delocalization characteristics of regioregular high mobility polymers.

Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. This work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties

Enterococcus faecalis Adapts to Antimicrobial Conjugated Oligoelectrolytes by Lipid Rearrangement and Differential Expression of Membrane Stress Response Genes.

Conjugated oligoelectrolytes (COEs) are emerging antimicrobials with broad spectrum activity against Gram positive and Gram negative bacteria as well as fungi. Our previous in vitro evolution studies using Enterococcus faecalis grown in the presence of two related COEs (COE1-3C and COE1-3Py) led to the emergence of mutants (changes in liaF and liaR) with a moderate 4- to16-fold increased resistance to COEs. The contribution of liaF and liaR mutations to COE resistance was confirmed by complementation of the mutants, which restored sensitivity to COEs. To better understand the cellular target of COEs, and the mechanism of resistance to COEs, transcriptional changes associated with resistance in the evolved mutants were investigated in this study. The differentially transcribed genes encoded membrane transporters, in addition to proteins associated with cell envelope synthesis and stress responses. Genes encoding membrane transport proteins from the ATP binding cassette superfamily were the most significantly induced or repressed in COE tolerant mutants compared to the wild type when exposed to COEs. Additionally, differences in the membrane localization of a lipophilic dye in E. faecalis exposed to COEs suggested that resistance was associated with lipid rearrangement in the cell membrane. The membrane adaptation to COEs in EFC3C and EFC3Py resulted in an improved tolerance to bile salt and sodium chloride stress. Overall, this study showed that bacterial cell membranes are the primary target of COEs and that E. faecalis adapts to membrane interacting COE molecules by both lipid rearrangement and changes in membrane transporter activity. The level of resistance to COEs suggests that E. faecalis does not have a specific response pathway to elicit resistance against these molecules and this is supported by the rather broad and diverse suite of genes that are induced upon COE exposure as well as cross-resistance to membrane perturbing stressors

Cholera- and Anthrax-Like Toxins Are among Several New ADP-Ribosyltransferases

Chelt, a cholera-like toxin from Vibrio cholerae, and Certhrax, an anthrax-like toxin from Bacillus cereus, are among six new bacterial protein toxins we identified and characterized using in silico and cell-based techniques. We also uncovered medically relevant toxins from Mycobacterium avium and Enterococcus faecalis. We found agriculturally relevant toxins in Photorhabdus luminescens and Vibrio splendidus. These toxins belong to the ADP-ribosyltransferase family that has conserved structure despite low sequence identity. Therefore, our search for new toxins combined fold recognition with rules for filtering sequences – including a primary sequence pattern – to reduce reliance on sequence identity and identify toxins using structure. We used computers to build models and analyzed each new toxin to understand features including: structure, secretion, cell entry, activation, NAD+ substrate binding, intracellular target binding and the reaction mechanism. We confirmed activity using a yeast growth test. In this era where an expanding protein structure library complements abundant protein sequence data – and we need high-throughput validation – our approach provides insight into the newest toxin ADP-ribosyltransferases

A922 Sequential measurement of 1 hour creatinine clearance (1-CRCL) in critically ill patients at risk of acute kidney injury (AKI)

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Membrane permeabilization by conjugated oligoelectrolytes accelerates whole-cell catalysis

Conjugated oligoelectrolytes (COEs) boost the electrical performance of a wide range of bioelectrochemical systems, yet their mechanism of action remains incompletely understood. One possible mode of action is that COEs permeabilize the cell envelope. We thus examined the effect of tetracationic COE, DSSN+, on the permeability of the inner and outer membrane of Escherichia coli by detecting extracellular activity of normally periplasmic and cytoplasmic enzymes. DSSN+ increases the release of the periplasmic enzyme alkaline phosphatase (ALP) up to 20-fold, but does not significantly change the release of the cytoplasmic enzyme β-galactosidase. Additionally, DSSN+ caused a 2-fold increase in the turnover of a cytoplasmic substrate. These studies present a more complete understanding of the mechanism of action in bioelectrochemical systems and pivot future applications of COEs towards a method for improving whole-cell catalysis

Understanding Energy Loss in Organic Solar Cells: Toward a New Efficiency Regime

Reducing energy and voltage loss is an imperative area of improvement for the design of organic solar cells (OSCs). Both in the context of charge generation and charge recombination, significant amounts of energy are lost even in state-of-the-art OSCs compared with their inorganic counterparts. Through a set of recent examples, however, we show that (1) charge generation can proceed with high quantum efficiency even in the absence of an offset energy at the donor-acceptor interface and (2) non-radiative charge recombination may be mitigated by considering systems with distinct properties of the interfacial charge-transfer state. To capitalize on these recent advances in understanding, we provide three actionable paths forward that aim to better identify, process, and characterize low energy loss systems: incorporating consistent and accurate measurements for energy levels, moving away from photoluminescence quenching, and exploring blends with reduced miscibility.S.M.M. and R.H.F. acknowledge support from the KAUST Competitive Research Grant Program (grant number 2275). N.A.R. and G.C.B. acknowledge support from the Department of the Navy, Office of Naval Research (award numbers N00014-14-1-0580 and N00014-16-1-25200)

Charge delocalization characteristics of regioregular high mobility polymers.

Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. This work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties